Crystallizing Self‐Standing Covalent Organic Framework Membranes for Ultrafast Proton Transport in Flow Batteries

Abstract Covalent organic frameworks (COFs) display great potential to be assembled into proton conductive membranes for their uniform and controllable pore structure, yet constructing self‐standing COF membrane with high crystallinity to fully exploit their ordered crystalline channels for efficient ionic conduction remains a great challenge. Here, a macromolecular‐mediated crystallization strategy is designed to manipulate the crystallization of self‐standing COF membrane, where the −SO 3 H groups in introduced sulfonated macromolecule chains function as the sites to interact with the precursors of COF and thus offer long‐range ordered template for membrane crystallization. The optimized self‐standing COF membrane composed of highly‐ordered nanopores exhibits high proton conductivity (75 mS cm −1 at 100 % relative humidity and 20 °C) and excellent flow battery performance, outperforming Nafion 212 and reported membranes. Meanwhile, the long‐term run of membrane is achieved with the help of the anchoring effect of flexible macromolecule chains. Our work provides inspiration to design self‐standing COF membranes with ordered channels for permselective application.